THE  ADDITION  REACTIONS  OF 
PHENYLPROPIOLIG  ACID 


BY 


RUPERT  SAMUEL  DANIELS 


THESIS 


FOR  THE 


DEGKEPJ  OF  BACHELOR  OF  SCIENCE 


IN 

CHEMISTRY 


COLLEGE  OF  LIBEJiAL  ARTS  AND  SCIENCES 


UNIVERSITY  OF  ILLINOIS 


1922 


Digitized  by  the  Internet  Archive 

in  2016 


https://archive.org/details/additionreactionOOdani 


) 922 
X)22 


UNIVERSITY  OF  ILLINOIS 


_ _ ^ .25.  r J-2  2Z 192 


THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 

iiy-n®  r_t!_  aTiUPJl  _ i§3-_s 


EN^tttfd  S!he  Addition  React  long  of  Phenylproplol  j,c  Ac1rl. , 


IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 
DEGREE  OF 


Instructor  in  Charge 


Approved  : 


HEAD  OF  DEPARTMENT  OF 


5 0 jl  ,rS*i 


7'7^  f • 


ZIOVIUJI  TO  YTlfiSjVIWy 

\ 


1 

■\  ',.  ».v 

'■  IBl'* 

■i  . ■■  “ ~il 


- "I 
»-  J 


. .V.'* 


’ i 


^.  vtfr'  r’.  ^ 

■i  ■"  v« 

- “ ■■  ■ .,  ■.'  i! 


^ .Yfj  ^i4  V^itv'i'Kh;  ;jt  &mx 


is;"'-' 


-.i  - ^ 

- .4  **-— — --  ^ y*yf  ‘--^1^  - « ■*••  - - . ' * «lf 


k^r'.  ,J 


fpi 


^:l 


^.5>' 


' V * > . 


i.u^.  ,a 


3ii<  ‘*<>  f^iUV'  r-j  ha  ilK/fiTOT/Oftl^X^ 


K'J 


^ • *iS’ 


-4f  • * • ;<3ISK^*<iSB!^-’'^  *••  i.?^Li:^wvv.  'K>  aa^slxsKi  f* 


■'If'i  I . ■'.  * 


“**  rti  ’ • " 

uT  -xv ' '■  . ' 

- . ■ ■•  u-<"  ' . 

^ - * •*  • - 

V 


I. 

TABLE  OF  COITTEITTS 
Introduction  and  Historical 

Page 

1 

II. 

Theoretical 

5 

III. 

Experimental 

8 

A.  Preparation  of  Phenylpropiolic 

Acid, 8 

B.  Preparation  of  the  Ethyl  Ester 

of  Phenyl 

propiolic  Acid. 

16 

IT. 

Summary 

18 

Y. 

Bibliography 

19 

-1- 

IITTP.ODUCTIO:^  AKD  HISTORICAL 

Phen^?’lpropiolio  acid  has  been  known  for  more  than  fifty 
years.  It  has  been  a suoject  of  interest  due  to  its  great  re- 
activity. next  to  orthonitrophenylpropiolic  acid,  it  has  been 
the  most  investigated  of  the  acetylenic  acids,  orthonitophen^ro- 
piolic  acid  being  used  at  one  time  in  the  synthesis  of  indigo. 

The  unsaturat ed  nature  of  phenylpropiolic  acid,  makes  it  very  un- 

staole,  so  its  preparation  xs  not  an  easy  Ane,  The  grouping  — C3C— 

0 0 

is  unstable,  like  - C - CEg  C - OH. 

Phenyl  propiolic  acid  and  its  esters  have  been  used  prin- 
cipally in  condensation  reactions.  It  condenses  with  itself  to 
form  naphthalene  compounds.^  The  esters  condense  with  diketones 
and  substituted  diketones,  to  form  pyrones^,  they  condense  with 
hydroxylamine  to  fono  isoxazolines^,  and  they  form  addition  com- 
pounds with  malonic  and  scetoacetic  esters, 

Glaser  , first  prepared  phenylpropiolic  acid  by  passing 
carbon  dioxide  into  an  alcoholic  solution  of  3—bromstyrol  contain- 
ing a little  sodium.  The  acid  was  recrystallized  from  ?;ater  or 
sulphuric  acid. 

0 

CeHgCHiCEBr  - 2Ha  - OOg  C^IgOrC-C-OHa  - HaBr  - Hg 
He  also  prepared  it  by  using  phenylacetylene  in  place  of 
B-bromstyrol. 

0 

^C^E^OSCE  - 2Ha  - 2C0g  2C6K5C5C-C-0Ha 

Ehrlenmeyer^  used  B-chlorstyrol  in  place  of  B-bromstyrol 
used  by  Glaser.  A comparison  of  yields  was  not  possible. 

Barisch®  prepared  phenylpropiolic  acid  by  treating  a-brom- 
cinnamic  acid  with  the  theoretical  amount  of  alcoholic  potash.  He 
also  prepared  it  by  treating  3-bromcinnamic  acid  for  a longer  per- 


■■  » '.■  » V ii-»/ 

II 

■.( 


0 


1 


j 


-2- 

iod  with  alcoholic  potash. 

In  1884  Perkin’^  made  the  first  complete  study  of  the  pre- 
paration of  phenylpropiolic  acid.  He  used  two  principal  methods. 
The  first  method  was  to  hrominate  cinnamic  acid, and  then  to  treat 
the  dihromcinnamic  acid  with  alcoholic  potash.  This  process  gave 
a-£.  h-  hromcinnamic  acids  (mono)  , which  were  separated  hy  their 
ammoniium  salts,  the  a-monhrom  ammonium  salt  heing  the  less  soluhle 
The  h-acid  was  then  converted  into  the  a-acid  hy  heating  just 
above  its  melting  point,  or  by  esterification,  in  which  case, 
the  ester  of  the  a-acid  was  formed.  The  a-ester  or  acid  was  then 
treated  with  alcoholic  potash,  and  phenylpropiolic  acid  was  ob- 
tained. The  yields  by  this  method  v;as  better  than  by  any  of  the 

preceding  processes,  already  given. 

0 0 
CgEj,CH5CHC-0E  - Pro  ---  CgEgOEPr-CEBr-C-OE 

0 0 

2C.EoCH3r-0E3r-C“0E  - 2E0E  — CgHpC-BrzC-lsC-OE:  -2KPr  - HoO 
6 5 g ^ ^ 0 

C.E.CErCBrC-OE  — -fheat^  CcE^C3r=0H-C-0E 
Cgnj!?3r=CF-0-0H  - rOE  — OgEtCSC-O-OE  + 

The  second  method  used  was  a modification  of  the  first.  It 
consisted  of  forming  the  ethyl  ester  of  cinnamic  acid,  brominating 
it,  and  finally  tresting  the  dibrom  cinnamic  ester  with  the  theo- 
retical amount  of  alcoholic  potash.  The  phenylpropiolic  acid 
was  recrystallized  ifttm  water,  and  the  yield  was  B0-86f^  of  the 
theoretical. 

0 0 
CgEgCEzCHO-OH  - Gj^HgOH  -fECl  gasj  C .H5GE=GEC-0B255-  EgO 


Cgfij^CEBrCHPrC-OCgEg  - SHOE  — ~ CgF.gCsCC-OE:  - CHBr  - SEgU  - 

0 0 *^2^£GE 

C^RgCEsCHC-OGgHfe-  GeH5OrPrCEBrC-0C2E5 

If  an  excess  of  alkali  was  uSed  the  follov/lng  reactions 
took  place: 


. . 


-L 


r 


1 


I 


i 


-3- 


p 

+ FOH  — »•  CgHpCHC!!  t 

0 pr 

^.EuCSCC-OX  + 2E0II  — ^ CeHsCrCEo-#:  E0CO3 
/OE 

(CgEgCrCHg  + HCl  — ^ 

In  1891^  a change  v;as  made  in  the  preceding  method,  an  eX' 


cess  of  potash  was  used  and  the  time  of  reaction  reduced  from  6-8 
hours  to  4 hours*  The  yield,  based  on  the  ethyl  ester  of  diorom- 
cinnamic  acid, were  90-96^'  of  the  theoretical. 

Michael^  recommended  the  preparation  of  a mixture  of  a-  and 
b-  bromailo cinnamic  acids,  by  the  action  of  dilute  a(iuaeouE  alksvli 
(£•5  moles  for  each  mole  of  acid^  , and  subseQ.uent  transformation 
of  the  mixture  into  the  a-brom  acid  by  heating  for  a moment  just 
above  its  melting  point.  The  a-brom  acid  was  converted  to  phenyl- 
propiolic  acid  by  heating  for  4 hours  in  a water  bath  with  ZOf. 
aquaeous  potash  solution.  The  yield  was  85f^  of  the  theoretical. 

Sudborough  and  Thompson^®  showed  by  experiments  that  the 
employment  of  aquaeous  alkalis  tended  to  form  -bromcinnamine , 
especially  if  the  temperature  was  not  carefully  regulated,  also  tha-; 
the  transformation  of  the  a-brom  alio  acid  into  the  a-brom  com- 
pound did  not  take  place  so  readily  as  was  stated  by  Michael.  The 
following  method  v/as  adopted  by  them:  hioromocinnamic  acid  was 

shaken  in  the  cold  with  alcoholic  potash  f£moles^,  the  alcohol  was 
removed  by  evaporation,  and  the  two  a-brom  acids  wrere  separated 
by  the  aid  of  their  salts*  The  a-brom-allo  acid  was  crystallized 
from  a mixture  of  light  petroleum  and  chloroform,  and  then  trans- 
formed into  phenylpropiolic  acid  by  heating  for  two  hours  on  a 
water  bath  with  ZOfo  aquaeous  potash(£.b  moles).  The  acid  v/as 
crystallized  from  chloroform,  and  the  yield  was  68-70^  of  the  the- 


oretical. 


/ 


• O It 


-4- 

Sudborough  and  jamesH  prepared  phenylpropiolic  acid  from 

the  dichlorocinnamic  acid  on  treatment  with  aquaeous  potash  at 

100°C  for  eight  hours.  The  yield  was  bOfj  of  the  theoretical. 

The  methyl  ester  of  phenylpropiolic  acid  was  prepared  by 

Liehermann^^  by  passing  dry  hydrogen  chloride  through  a solution 

of  phenylpropiolic  acid  dissolved  in  absolute  methyl  alcohol. 

The  ethyl  ester  of  the  phenylpropiolic  acid  was  prepared 
13 

by  V7.H.  Perkin  by  a method  similar  to  that  used  for  the  methyl 
ester. 


-5- 


II.  TEECEETICAL 

In  consideration  of  the  different  methods  of  preparation  of 
phenylpropiolio  acid,  it  was  decided  that  the  Perkin  method  ap- 
peared to  he  the  best.  A detailed  study  was  undertaken  with  the 
hope  of  perfecting  the  method  of  preparation  and  ultimately  in- 
creasing the  yield. 

According  to  Perkin,  who  used  ether  as  a solvent,  for  bromin- 
ating  ethyl  cinnamate,  the  addition  takes  place  instantly.  K0W7 
ever  it  was  found  that  the  reaction  proceeded  much  more  slowly 
than  he  indicated.  The  formation  of  a lachrymafcor  made  the  handling 
of  the  product  disegreeable , so  chloroform  was  substituted  for  the 
ether,  and  no  lac^ijmetor  was  formed.  A,  slight  disadvantage  was 
that  the  chloroform  did  not  evaporate  as  completely  as  the  ether, 
but  could  be  removed  under  diminished  pressure. 

Perkin  obtained  the  dibrom  ester  by  spontaneous  evaporation 
of  the  solvent.  "Since  the  amount  of  ester  was  not  accurately 
known,  if  the  theoretical  amount  of  bromine  were  added,  the  pro- 
duct was  alw^s  contaminated  by  it.  So  the  ester  was  washed  with  a 
sodium  bisulphite  solution  to  remove  the  excess  of  bromine,  and  then 
washed  with  sodium  carbonate  solution  to  remove  the  acids.  A.fter 
washing  once  with  water  and  drying  the  solution  with  calcium  chlo- 
ride, ethyldibromoinnamete  was  obtained  in  the  foim  of  slightly 
yellow  crystals  by  evaporation  of  the  solvent. 

The  effect  on  yields  of  the  different  concentrations  of  al- 
coholic potash  was  next  studied. - Perkin  stated  that  the  theoreti- 
cal amount  of  potash  was  used,  but  did  not  give  the  quantity  of 
alcohol  in  which  it  was  dissolved.  V/hen  95f!  alcohol  was  used  it 
was  found  that  the  quantity  had  little  or  no  effect  on  the  yield. 


. ■ ■ f 

\ ^ ^ ctTC 


f 


♦ ■ . . ' ■ -i  V 


/ 


j . 


■ j 


•.r.' 


0 . . 


-6- 


The  potassium  hydroxide  obtained  from  the  storeroom  varied  in  com- 
position so  the  approximate  emount  of  this  potash  was  dissolved 
in  alcohol,  and  then  See  of  this  solution  was  titrated  with  stan- 
dard acid,ECl.  Sy  this  method  the  theoretical  amount  of  alcoholic 
potash  was  added  to  the  dibromester.  The  yield  of  phenylpropiolic 
acid  was  no  better  ‘ when  the  theoretical  amount  was  added 
than  when  the  approximately  correct  amount  was  used. 

The  effect  of  an  excess  of  potash  on  the  dibrom  ester  was 
then  studied.  Increased  yields  were  obtained  when  an  excess  of 
potash  was  used  and  the  time  of  reaction  shortened  to  4 hours. 

The  best  results  were  gotten  when  one  and  one  half  times  the  the- 
oretical amount  of  potash  was  used.  TThen  twice  the  amount  was 
added  e large  quantity  of  phenyl  acetylene  was  produced. 

Uhen  the  alcohol  was  distilled  from  the  potassium  bromide 
and  phenylpropiolate , there  was  some  decomposition  of  the  latter, 
near  the  end  of  the  distillation.  This  was  prevented  by  filtering- 
off  the  precipitated  salts,  neutralizing  the  solution  with  hydro- 
chloric acid,  and  then  distilling  off  the  aJ.cohol. 

Perkin  dissolved  the  potassium  salts  in  water,  and  acidified 
this  solution  with  dilute  sulphuric  acid,  precipiating  the  phenyl- 
propiolic acid  as  an  oil, which  solidified  onns tending.  The  crude 
acid  was  then  filtered,  washed  with  water,  dissoved  in  sodium 
carbonate  solution,  this  was  gently  heated  with  animal  charcoal, 
filtered,  and  acidified  with  dilute  sulphuric  acid.  f?everel 
changes  were  made  in  this  proce  dure.  After  dissolving  the  salts 
ina  water  the  solution  was  extracted  with  ether  to  remove  any 
phenylacetylene  and  brornhydrocarbons  v/hich  might  be  present.  The 
' solutionnwas  then  heated  with  animal  charcoal,  filtered,  and 


wo 


■ ::>  u. 


,vr,t 


' ■ ■ u 

.-■■■ 

■ j . , . 

. / . ‘J*  Q -»  • 

'f* 

: r: 

‘ ‘ * 1 

. . 1! 

- r-.'  l>  ’- 

’uV  r?^-, 

< *'  .'il 

)C‘*  ^ ■ 

■ vv;  _ SI . 'io  ""  ■ :':  ■ 

'r\ 

, "■(  1 * , ■ 

'.  J r . 

"»■ 

•■■.■■'lOi.r  , : iL 

1 s.  r;  ' ' ' 

« 

■ ' ■ : : aYi 

* )' 

■^V , / 

' / .i  ‘ . ' 

■K  ■.  ,//'  tJiCiO 

:v 

.'‘Mr.,  ^ t 

'■'  '*■'  o.l\ 

' ! 

'.A'-.n 

'..r  '■,  V 

J’fwoir  ‘ 

jr 

■:■  .’'t,  ''  ’ ■;.:l’'  > 

' .f 

» r • ^ 

"■  ■ ’ J il*- 

;.'  . ;.,  :;y 

n 

■ <*  1 

\ I I 


V : •-,  i}^-‘  r : 

• ■ -i.  ....,  -,r, 

- ^ . -'  'v  f.,  y.:.'  ‘ , ■ ' ■S  ' . i 

I'o  X ifejjjiij  \’  ,'  v*  ..  ■ ..  I,'-: 

r I T '■•Ti*  . : f ; 

;■  £ ‘I : ' i ,j;  / j • 

• f.  ; 'Xr-  ■ It/  vij’O'.-'XT  •:')  r ■ 1 i.'.,:^ 

:■'.  Jv.£  ;-.v  V'"  uc,!:- 

. . '0  J!  i ' ■ .-f  ; 


, ..u  iiii/.f  . 


T .1 


; / 


i:  i 


iTx 


5/ 


■>.!■-.>•  . V., 


-7- 


aoidified  with  dilutfe  hj^^drochloriG  soid.  It  was  found  that  the 
charcoal  had  little  or  no  effect  on  the  quality  of  the  product  ob- 
tained, and  its  use  might  he  omitted  from'*1;he  ahovd  proceedute. 


I 


' ’■  ' • ' k •<»  y'  ,.t''  ,-  ••  _ '.'J4  ■ , 1 -.  ■ ■'‘r 

I*  ^ .<J'firD,>yt;6'r 


« Otf  ^ 'J  4 # CJ  -4i  ,1  kW  /4«JUJkf  ^ ,‘^jj  ^ ^ A *?  J.  t?*©  i1 

'■  ^ ' ^ ' -T-^  * ■'  - r,  ' j 

'•■jrmiD  r.  ‘ \ :■  ' 'Vk*;w  ' 


I 


w 


'./I 


!■  ai^^ 


mu 

i * 


f/' 


;t. 


v^.v  ''i 


■■  ''  'V  ‘ . S,Si 

■ '■:*  ' -7  ’ ?■ 


iW  • • ■'  i' 


'•%.  ■'■ 

. 


>'V 


, - \ 

' t i’ ' 


VT>  ,,  r ■ 

ii‘  „ ■■ 


v,'  .,,■«  ' • ^ AV,;i?(l|j^^ 


J ,»  \ ' r': 


.,■>,.  .-’Sipfiser'  ■’ 

7 I ‘ 


* 't 


. . . fife' ^ 


A 


B - 


af.  : y,^- 

^ #fe. 

* ' • ' IW' • ‘a 


•v'vrwff'-'j 

* , i <V^;^ 


<Hi 


*•■•.', V, 


-k 


■ - H'-hi 


rtiM 


« 


I* 


II  . ■ ■ . ■ Wl  ■ • ‘‘I 

' \'»r  •-,'  . ' ^''i  ' 

•^•■'W.  T - , .''jA  ■ ' - !vSi(.*?4 



? 'gAMiy!  garj-j,  j;  tgyr»:4gr^»^.Terg.:*a^^ 


ii' ' ' ' fe 


a ^ fA  ’; 

. At  .1  Itf 


Ill 


-a- 

expe‘rbie:!IIAL 

A.  Preparation  of  phenylpropiolio  acid. 

Experiment  #1 

The  method  of  W.E.  Perkin  was  used.  50  grams  of  cin- 
namio  acid  was  suspended  in  100  cc  of  absolute  ethyl  alcohol  and 
dry  hydrogen  chloride  was  passed  through  the  solution  until  the 
liquid  was  thoroughly  saturated.  The  solution  was  then  placed 
in  a stoppered  bottle  end  allowed  to  stand  over  night  to  make  sure 
that  the  repction  was  complete.  The  product  was  then  poured  into 
ice  and  water,  the  oil  which  sank  to  the  bottom  separated  by  means 
of  a separatory  funnel  and  the  aquaeous  liquid  extracted  with 
ether.  The  oil, which  was  almost  pure  ethyl  cinnamate,  was  dis- 
solved in  ether,  washed  with  a dilute  sodiom  carbonate  solution 
• 

to  remove  ell  traces  of  hydrochloric  acid  and  unchanged  cinnamic 
acid.  After  drjj^ing  over  calcium  chloride  it  was  treated  with  18cc 
of  bromine  in  small  quantities,  care  being  taken  to  keep  the  liquid 
cool.  The  bromine  disappeared  rather  slowly  without  evolution  of 
hiydrogen  bromide*  After  standing  for  a short  time  the  product 
was  poured  into  a large  open  dish  and  the  ether  was  allowed  to 
evaporate.  The  ethyl  ester  of  dibrompropionic  acid  separated  in 
large  crystals,  foiuiing  a solid  cake  in  the  bottom  6f  the  dish. 

The  crystals  were  pressed  between  filter  papers  and  exposed  to 
the  air  for  a short  time  to  remove  traces  of  bromine.  The  yield 
of  the  dibrom  ester  based  on  the  cinnamic  acid  used  was  77f  of  the 
theoretical. 

87.4  grams  of  the  dibrom  ester  were  divided  into  two  portions. 
The  first  portion  was  added  to  an  approximately  normal  solution 


i 

l! 

. ' ci.  r'.vl5  0’-x;.'.r 

■vT-r  -:(> 

1 

- ■ ■■;  / G ; 

1 ( 

. ■'  ■ ri  ; 

*;  Otlo;  Jt  r^i.G. 

> .*  1'  ■ 0 C f/  ' • 

.».■  i>0  ■■  •'  T>  ,:i;  •;  r'l'  '..I'w!  O.L 

:;  -J  : ‘ : j ' . - "yC' 

I •■  ; r.t,  ' " " r 

•;  -V  ■-•.■  i.'C' 

- t.  » \ 

\ ■ *,...0'^^  : :••  • '1 
ll' 

• >•  1 . ,1 

) 

•vti-'.  y: 

"0 

'.'•J  >'r.  •/  Su  ■.' 

0^;-  ; ^ ‘ ■■■  : . i: 

n ^ , 

. C"'  > . ■'  -,.'l  ; iJfVJ  -lO;  • • ■ ‘ , -I-  : 

'k 

* -•  '-0  'C  { »i_T|  ',  y. 

~ ' ■ , : ’ . ■ * ‘ u 

' '’if  - . t 

ol  - :.'.o  '.'  l;c 

• . y 

r;)  ^ f ;•  ■ ^ I i^ry,'),/ 

o,:”'  ro  Vi  (l:^  LurS'  t , 'vr',  j 

- •*  ^ *■  ■ 'I  i"f  ’ •'  i;^i  c V- 

'■  ' ■ -j  ir.  .6%-  )ii 


. ' . ••  t-v-.-c  >y  ii;s  ■ la  OT  oiyt  ..J’JF«'^:^ 

• • oiliV ■' .Ijii;  , w,  '■  Ua.Q’ 9yi 

’ ■ 

<•71 

■V  .-foi  , 4 '*>  . 

• . ■■' 0*).^  ■ , r .^-.rrC‘; 


:y,_.  ic 

-.Sm  'vr.vx^*.  07 

c^' 

• , 

TuVO 

ii'a 

.•'  1 .‘iM 

• ;..i  vr'Ji^r-'ci  'ic 

•/■vr'  ; , ;■ 

. ;. 

* ' • • -1  • 0 -J/ 

•'•'•-'f. : ■ -i-i.-'*"  o.‘ : •;  ; ;• 

>t  T:  ,'(OM  i-i-  i.'-Ci'' •'•r  j. 


n'b 


• iV 


I 

1 


5 


•.6 


C" 


3 j i ' 


U ,'iC/ 


C • !•’•*- 


i ' '■-'•  '••  lX«i  ■'fiX'-.* 

: »■-•  . ' OtU-- 

. / ■ . ... 

11 

•■’  . i ]-.r  V c ■ ' '■  ';.i. 


»Vi  i J.  "OJI  r V.;’vv'  !' 
■ * • r-=-r 


,/:  . ' ui;  {. 


i -•'“T  5.' 


, , , ' ‘ 

. *JI*  r.-i  '/ii  . ■ ;.-Lr*  -•  ' ' AA  ..  J* y. ' I 


r- 


ji 


-9- 


of  alcoholic  potash  f 1 mol  of  ester  requires  3 mols  of  potash)* 
The  second  portion  was  added  to  a trice  normal  solution.  In  each 
case  the  reaction  was  so  energetic  that  the  heat  evolved  was  suf- 
ficient to  cause  the  alcohol  to  boil.  As  soon  as  the  ester  had 
been  added, each  portion  was  heated  to  boiling  for  six  hours  in 
a fiask  connected  with  an  inverted  condenser.  The  alcohol  was 
then  distilled  off,  and  the  residue,  which  consisted  of  a mixture 
of  potassium  bromide  and  the  potassium  salt  of  phenylpropiolic 
acid,  were  dissolved  in  water,  and  the  solutions  filtered.  The 
solutions  were  acidified  with  an  excess  of  dilute  sulphuric  acid 
which  precipitated  phenylpropiolic  acid  as  an  oil  that  solidified 
on  standing.  In  each  case,  the  crude  acid  was  filtered  off, 
washed  well  with  water,  dissolved  in  sodium  carbonate  soiLution, 
and  gently  heated  for  one  half  hour  on  the  water  bath,  agitating 
well  from  time  to  time.  After  filtering  off  the  charcoal,  almost 
colorless  solutions  ofthe  sodium  salt  were  obtained,  which  on 
acidifying  with  dilute  sulphuric  acid  precipitated  the  phenyl 
propiolic  acid.  The  acid  was  then  recrystallized  from  water. 

The  yield, from  both  e±periments,  of  phenylpropiolic  acid  was  very 
poor,  and  a 3eilstein  test  shov/ed  the  presence  of  halogen.  A 
melting  point  of  the  acid  proved  conclusively  that  there  was  pre- 
sent some  raonobrooinnamic  acid.  The  acid  obtained  when  a twice 
normal  solution  of  alcoholic  potash  vrae  used,  v;ae  the  more  pure. 
When  the  acid  was  recrystallized  from  water  a residue  remained 
which  was  probably  phenylacetylene. 

Experiment  §2 

The  same  general  proceec^ure  was  followed  as  in  the  pre- 
ceeding  experiment. 


js&Ar^iriaai 


nJc.  ^ 


■’  Ti'i  ■' 

1 . f.  «.'  •>  ':  V 

• f • • ■ ''  ; ' 


'V  J-  ' td  .r-o,r  r ' .f.-; 

’ '■  .’  ( ■::  j."  : 

''  C'l;  ' ■■  . 


'U  O'.'iT  • • iCO 


■■  ^ :•  "in’" 


. I '''''.•  o 


•::>  ■' 


■•■  0 ^,i,  .';■■■  >-^r. 

M 


'\  ^ tj . ■ 


! i 


i 


. C JO’.i  ' 


.■'* 


V? 


v^“  Ji  - ■ 

oil'  -l-.i  ■ >■  jf  - • 


, .:.j.‘.'i  »i  0 ' *■ 


j ^ ii  i . ’ C V i’.j  -f 


V I 

I j 


:.'  f ' . ■*  ! 0 c:  ■■  ■ j uic ’ f*  > r i '’.te  <>  1:  c 


; Tia...  , 'i>'  \hs\9  K .' 


^ I , *V/,'  * 


, io-:* 


1 I 

) ( 

i 


■ t 


r;l'^  .r-.  : 


I 


V >>v»  i . r sT T*«t  : u*  f *).' X 0 

•■'  ' • '■  ■•  A ,y  ;•'•<  •:  , »'oX-:.  ' 


V 


I 


n'_*  : _1  J'  j 

' ^ 7 w.  ilUX*l;<3C 

, ■ : i;  v:  re-  ' 

'•r  o o ^ ‘ ■■■11' 

, J .<•-,■•  V-.., 

■ ' . . /'  “I ) I'  i;  '\  I V*  »'i'-  ■ 'j  < ''.' 

? • ■■  n:  b.t  . * •( 

. ( : . f- V-  ■ . 

'-■  : ' T^'.  ' ■.*•.. -f  ;l  ••/■■:;/ ut:^)  'ir'vci'c;' 

• ■>;,'  '1 -Mfi  ■<v-<4.c  1‘iX ’'v»'  iu,r ' . f;c' 


3,.  ■■■  , , ■ ■ J’U  iU 


, ; X ■■•'  i--'  O?-,' 


• '5  ’• . >,v  ' . ' 'ii  .'• 

‘sT  ' 


ro 

l\kX  . ' 


\V! 


' .t 


r 


w/i  r , .;aoX'^"-V  r> 

7' i';|,  aji-'  ,,£txv  ' 

f,  t>  »'f  . . (,.  Y'X^Ci'‘£>T 

":c. ' .'■  ■ . ■ 


^^■  ';.•.  ' , •;i"  -.-"tc  'j  rt't  V » , 


■'  .■'»•;  ““OY 


'J 


• O.iV  •:■ 


■■  ■ i !>:■ ''ooX' ■ '*.n  nt  j.  ci ' f“  'iCi: 


>♦.‘•>,1  fijfri’t  •'.■:  •,•?  4|J  't-y.K''  C7' 


I t r * 


1 


t \ 

■•  CvgO'C''!.!!  ti 

: : .V  .;  V • 


"i-dlT  ■ X 10  I ‘ 


' -tX  '’i' 


. < 


•>  '■■  ■ ^ 1 


fii- 


■7i. 'V  0.*?  .'  ’* 

J y 

,*7.*>/-x«  '‘T  >ni7 ’7C.' 

■.:  !■  Bwawga 


Lii.w. 


-10- 


48  grams  of  oinnamic  acid  were  dissolved  in  lOOcc  of  absolute  al- 
cohol and  hydrogen  chloride  jjassed  into  the  soltition.  The  ester 
was  separated  and  18cc  of  bromine  added.  97.6  grams  of  the  di- 
bromo  ester  were  obtained,  which  was  an  89, bf  yield,  based  on  the 
cinnamic  acid  taken. 

53.8  grams  of  potassium  hydroxide  were  dissolved  in  486cc 
of  95^  alcohol  f approx.  2H  solution),  and  the  dibrom  ester  was 
added  to  this  solution.  The  reaction  mixture  was  refluxed  for 
several  days,  samples  being  taken  out  each  day.  All  the  samples 
shov/ed  the  presence  of  halogen.  28.5  grams  of  crude  phenylpro- 
piolic  acid  were  obtained.  I'ost  of  this  was  used  in  trying  out 
various  methods  of  crystallization,  so  no  data  was  obtained  as  to 
the  amount  of  pure  phenylpropiolic  acid  formed. 

The  potassium  hydroxide  obtained  from  the  storeroom  varied 
in  composition  from  time  to  time  so  that  it  was  thought  advisable 
to  find  out  just  what  effect  this  had  in  the  results. 

In  the  next  experiment  the  potassium  hydroxide  was  dissolved 
in  9Uf  alcohol  and  then  5cc  of  this  titrc.ted  with  standardized 
hydrochloric  acid  to  determine  the  normality  of  the  soli:>.tion.  In 
this  way  the  theoretical  emount  of  potash  could  be  added. 

Experiment  #3 

49  grams  of  cinnamic  acid  w-ere  dissolved  in  100  cc  of  ab- 
solute alcohol,  and  the  ester  separated.  16  cc  of  bromine  were 
added  to  the  ester.  A slight  modification  was  made  in  the  method 
of  Perkin  in  that  chloroform  was  used  as  a brominating  medium 
in  place  of  ether,  because  ether  formed  a l-a.chi3m.ato:f, (probably 
BrCH2CH20CE2CE2S^  CH2BrCE0  from  the  alcohol .present ) . 


S*  ■ I . ,'(ii 


.i  . .'..iJ 

' p -'.  ‘r-v 

- . i'l  '-L 

• 

liV,  /. 

,. 

...  ■,  1*'.^  ' o' 

.f ..  . .'  ■ .■  ..»  . 

J ■ . 'f  ’ ' 

.'■>.'  -1 

-V  pi 

, fr:,  : 

'll  . 

, , ; . • O'fiJ  ; .' 

y£:|r'/«n  o “‘j’ 

' . c 

•I|  J -V 

_ <., ..  r . ~ 

< 'O  A '•■  >■•: 

.^s 

« 

. ' - t ^ 

; , ..  ■. 

i'  ^ ^ cli  ■ )' 

1 • - ■ r( 

'■  > 

' A- 

yiox  ■ )X 

•>:.X  - / ■;r:  ...'•. 

'■ 

'■  1 ':■  . ■ ii’  4' 

r , . . 1*  - ‘-  ■ 

^ i . .1  V ■ J 

, . . 4.  . , 

s ■ .:  D f, 

. ■ , ‘ .j  ■ 

i * * i 

‘X'"'  ';;i  .<  ! 

4 

'■.).frr  --r  .V7 

• “ . ■* 

♦ 

* -t  .‘  .* 

. : 4 

^ , Ji  ' 

‘ • k • c< 

. ' ' J 

■•■  o». 

rO>.  ■ V:  .. 

. r ■ '■ 

.j  vsV^■ 

t 

. ‘7';'  ^ 

:<ir^r  ■ ,1  . 

p j •,  ._■,».  ,;  *■.•.• 

..  , 50'  i .’.f 

14;!  ^.-r  ’.  ICi’i  V ■ , ^ ;,7 

jrfj  U/j 

^ •:X<^  ' . ' t 

^ '*;i£  X t 

•t 

’ ' i 

'“?1' 

rfW?? 

•m  . • 

■•..JP 

j <'T  '■  / .j '.vr-  I'  .;  , .c  p'  **  ' . 

.;.  * ■-.'  >•.:•  ii;‘  - V Vi  be..'  X€»;lft« 

' , ."'j 

>W  ' 

' lo  cr/iX  ‘'ti 

Tw  I ;■  ■ , ■ ‘ ' 7-  ’ * ,:  ,'  oji-ti:' 

\ .i  t-'J  . v'  . 

< to  7^--;,  . 

v.;c':  . ■ ‘Ic 

•;•  • . ■ ■ -yj  c/i  '■  f'.'*  •-' 

' ''.V^'  i 

^ . X'  ' ■’;■■:*  . 'JB'ti’Y  I’" , 

::.:v:  ^ 

p • • Ir'  I (*.  ^ ’ V^l  fi'  . 

• ■ “ ■ i 

'..  xw.'i.Cr  ■•-  53r;d;i;'..v 

X .:•  . *>  • u f ; . ; ,••?  (t:i 

/'  ' I ■'■  ■ ■''.  ■ '-viL 

' ''9  • i ^T(,  •'•:  ■ -yij  ' 

•(-  ■ t'./O  ■ T 

# 

i {■.;  >cf  ■/’; . J .‘■'i'aC  Vi- 

't-  :*~fi;:r.riT>c  \,  tfT 

i . 1 • pV  •»  Cii. -'■  X •• '-  »»  i 

^ ' .» i 

• ' . ^'  -n •./  >«»  c'.l  j ' icX  . -V  v,if 

' ' t 

■ I 


.*  j 

• ,/■  A A"'  ■ ■ ••■* 

K'r.:  \ i;, *^'Ur 

•':.'c'"tf‘'f:.QX,io  j.'i  "o 

.'©-s,.'-  Cf5.'  , ■ *>  ‘if  '(tXV 

X;'  : X'Tr  ^ '•[.'  •;/;  • , 

' iX  _ ,1 


11- 


After  'bromination  the  dibrom  ester  solution  was  treated  with  a 
dilute  solution  of  sodium  bisulphite  until  the  solution  was  a pale 
yellow.  The  acids  formed  were  neutralized  with  sodium  carbonate, 
the  aquc-eous  solution  separated,  and  the  last  traces  of  sodiuip 
carbonate  were  removed  from  the  dibrom  ester  solution  by  washing 
repeatedly  with  water.  The  solution  was  dried  and  the  chloroform 
allowed  to  evaporate.  The  dibrom  ester  was  crystallized  in  white 
crystals.  87  grams  of  the  dibrom  ester  were  formed  which  was 
78f^  of  a theoretical  yield. 

Experiment  f3a 

20  grams  of  the  dibrom  ester  were  treated  with  90cc  of  1.3IT 
solution  of  alcoholic  potash,  and  the  solution  refluxed  gently  for 
six  days.  Another  change  in  the  Perkin  method  was  made  l.ere.  Just 
before  adding  acid  to  the  potassium  pheny3.propiolat e , the  solution 
was  extracted  with  three  50cc  portions  of  ether.  The  solution  was 
then  boiled  to  remove  any  ether  that  might  remain  in  it.  In  this 
manner  any  unchanged  ester,  phenyl  acetylene,  bromhydrocarbons , 
or  acetophenone,  that  might  have  been  present,  were  removed.  The 
phenylppopiolio  acid  was  precipitated  v;ith  dilute  hydrochloric 
acid  instead  of  dilute  sulphuric  acid.  About  10  grams  of  the 
crude  acid  were  obtained.  There  was  e small  amount  of  oil  which 
was  insoluble  in  water,  which  was  probably  phenyl  acetylene. 

Experiment  #3b 

20  grams  of  the  dibrom  ester  were  added  to  90  cc  of  1.3H 
alcoholic  potash,  and  the  solution  refluxed  for  30  hours.  After 
extracting  with  ether  as  in  the  proceeding  experiment,  the  solu- 
tion was  boiled  with  charcoal  for  about 30  minuted.  The  charcoal 
v/as  then  filtered  off,  and  the  phenylpropiolic  acid  precipitated. 


• n 


r 

1 

5. 


y \ 


f 


i'.(.' .M  “-i  ••>('■  ,^  ,! 

. ' L'  • H'li; 

■ ,t  ,M 


:•  . H)  • ; 


i.  iO.' 


1 1 ' ■ . 


t - s ■• 


U-'i 


'•f  i..  O’.*.'-  • :,:c<)  .r,'«  t..;’  !• 

r,  ^ ^ g^fk  * tjQ-^  «> 

,'.r.  : 


l. 


V i'  '■ 

<» 


c c ■ 


. •i-"r 


. V ' 


':K 


.'  s 

'm 


"■  ‘ la 


' n ^ . to 


^■/ 


1-; 


(■  ’ !•>'■ 


-11.  I 


'»v,'  :■,  r.  f 


: ■>’•  [i 


. L'l 


' 

i. 


' 1 1 

1/  f 


" 'll  . .f  J -r^xo  ^ :.’.V 

t*'iX  ‘ j;  ■ vci'ti*x'h  ' liJl  r.eirl'J' 

■ . ' I*. ' ' 

, ■ '3(r.;:4o;  . . ..  ^v■»rrai^^J 

V .'  /.V  -L/'.  1 r-.-^o©f-  TO 

C.  I '.J.i'tj^..  , li  i.'*J  ., ' J jJ  .1,  > ,.  0 /,' ' . vv  ■’ 


rta^<'y  ' /i’lAui 


..I.  ' ..Yh  ' > 0 I 'iii.i  '.  X.:,TU 


r 


J ,r  .ii.i . ir' 


I TH'/ 


•I 


• iOM--  ' ; n :;’.r.\  .).rr  'Y  ’ 


i 

‘I 


- 'So  'f-jrli* 


- v'  j*.  /y  %/  * *^  *.  * 

^ ^ ' ■ iJt  i_^  J .. 


W.  i-‘. 


I , 


^•-.■r  T-  ,'.  1*1  ,-.  •*- 


li  , 


Vi  \i  ! 


vr 


'i;.. 


-12- 


The  crude  acid  was  then  recry stallized  from  v;ater.  3,8  grains  of 
the  pure  acid  were  obtained. 

Experiment  #3c 

The  same  amounts  of  dibromester  and  alcoholic  potash  were 
used  as  in  experiment  -,f3b.  The  mixture  was  refl'oxed  for  five 
days.  11.0  grams  of  the  crude  acid  were  obtained  and  5.4  grams  of 
the  purified  acid.  This  was  62.2  of  the  theoretical  yield. 

Experiment  #4. 

200  grams  of  cinnamic  acid  were  dissolved  in  300  cc  of 
absolute  ethyl  alcohol,  and  hydrogen  chloride  passed  into  the  so- 
lution. The  ester  was  separated  as  in  experiment  #3.  80cc  of 
bromine  were  added  to  the  ester  solution,  and  359  grams  of  the  di~ 
brom  ester  were  obtained.  This  was  an  QOfj  yield  based  on  the  cin- 
namic acid  used. 

Experiment  #4a 

25  grams  of  the  dibrom  ester  were  added  to  125  cc  of  alcohol 
containing  25  grams  of  potash.  The  reaction  mixture  was  refluxed 
for  four  and  one  half  hours.  The  proceedure  was  carried  out  the 
same  as  in  experiment#3b  up  to  the  point  of  recrystallization. 

10.5  grams  of  crude  pheniT-lpropiolic  acid  v;ere  obtained,  and  dis- 
solved in  a warm  solution  of  ZOf?  acetic  acid,  as  the  solution 
cooled,  it  was  diluted,  and  just  at  the  point  before  the  phenyl- 
propiolic  acid  came  out  as  an  oil,  a few  crystals  of  the  acid 
were  added.  Phen^rl  propiolic  asid  separated  in  perfect  needle-like 
crystals.  3.6  grams  of  the  pure  acid  were  obtained. 

Experiment  #4b 

100  gra.ms  of  the  dibrom  ester  were  added  to  500  cc  of  al- 
coholic potash  which  contained  100  grams  of  dissoivaBd  potash. 


■ r 


^ '’  .o‘  ’• 


i X :; 


:>c^fn"00S- 


-^^'jiiyjTTlIlfi  II 717 

W • 

V 


■ 

, ' ' ' 

‘ ' 

“^>.W  i1:.  /Cl 

; 

; 1^'  ./’  j,  f 

1 

'rj  *r/.  ’ ■ ' ' 

1 * 1*  . , ■ »■ 

,/..,y  '‘T.  j';;!.''': 

• 

• \ -C.4X:  * l-X  ) 

n i i ' 

• :'o  •■  ■ 

fi  : 

. •/■-;  i ::0  ..  V 

. : -.. 

« . k/ 

: . ■ -£.,  .•!  '• 

/ 

H' 

>1 

t 

V. 

■ -.  - ’ V*  *'•  . 

'• 

■ L 

. i ; ■■'•;.■  . ' : 

,:  ■ . .;,,  3J  ..' 

S • ‘s 

C-  ; , 

. *'  ' 

t;i_  , ' • ■•■''•ct  ' ....<y» 

. . ■'■  J 

V . ;iO 

j.. 

X.  . '1/..  t.:::..,.^  jun 

■ 

1 -■  J.  i.  ■'  1.4  . . 

, t?,:! 

•iv 

;JA  ' ^ t,?  r.  7 

:.  .rr;'';T i.' 

7, . . 

••inS. 

i .'; 

.i'  i.  "a 

> ' . / i/J 

/JS 

U'  oi4c/x- 

s 

‘ 

. ....'  i/f  [.C 

• . 

f.,  • 

1 

fee'  -V.  ...  . 

.'y 

-i  ’ 

ii. 

f'  . j ’ , ■ . » *J 

\i  .7'  .’  J .. 

....  . ./  ■ 

- . ;?!.  ;i!Mn  ,.t:  -5 

4 ,.  i'  iiicc 

■ .-i'. 

•v.  ♦ *• 

; ■ L'  C n! ' 

. ' C -i 

' . ■ t 1 

_l,  - • «'■ 

1 

■>'■  l;;Oi  .t 

’>  . I 


1 


■i  X'  xow  tivi 
, ,.r,_. ->.4. 


-!ur.  ..v  ' 

-r 

» f 

..>  J-.V  ' 


' I 


■ vXc/t). 

'•.vioc*. 


.'.ii  :'>e':s^-e . c 


' . • ■ ' . ; ' ><  '•  ■ ' > ' 

•X-  •>ii-.ri  • ;«■!  -iSri 


^ V'-  .; 

f - ' ■ 'f 


..Vi> 


to  J1ISI& 

M-!; 


,r: 


h 


m -»  ■■ 


M 


: f vf 


,0  •..  ■•  ^C:C  ■^^.  c 


I ■ j 


oi  ti; 


■•  ;o'’ 


The  reaction  mixture  was  refluxed  for  five  houre.  The  procedure 
was  carried  ou  the  same  as  in  experiment  #4a.  21.5  grams  of  pure 

phenylpropiolic  acid  were  obtained.  This  was  about  a 50f  theoreti- 
cal yield. 

Fxperiment  #4c 

The  same  quantities  of  material  were  used  as  in  experiment 
number  4b,  and  all  of  the  conditions  were  kept  the  seme.  22  grams 
of  pure  phenylpropiolic  acid  were  obtained.  This  was  of  the 
theoretical  yield, 

Experiment 

140  grams  of  cinnamic  acid  were  adcled  to  170cc  of  absolute 
ethyl  alcohol.  The  same  procedure  v/as  carried  out  as  in  experi- 
ment #2.  53cc  of  bromine  were  added  to  the  ethyl  ester  and  242 
grams  of  the  dibrom  ester  were  obtained.  This  was  a yield  of 

the  theoretical, 

Fxperiment  #5a 

The  same  amounts  of  material  were  usee,  as  in  experiment  ^4b, 
The  reaction  mixture  was  refluxed  for  five  hours,  and  apparently 
all  the  phenylpropiolic  acid  decomposed  into  phen^?'la.oetylene . 

Fxperiment  #5b 

The  same  amounts  of  material  were  used  as  in  experiment  #4b. 

The  reaction  mixture  refluxed  for  three  and  one  quatter  hours. 

After  the  alcohol  was  all  evaporated  off  not  all  the  solids  dis- 
solved in  water.  The  part  that  did  not  dissolve  ?;as  filtered  off. 
After  the  aquae oue  solution  had  been  treated  with  charcoal,  it  was 
acidified  and  allowed  to  stand  for  two  days.  On  filtering  an  oily 
substance , which  was  probably  phenylacetylene , went  through  the 
filter  paper.  15  grams  of  pure  phenylpropiolic  acid  were  obtained. 


.‘“It 


Lt"  0 ’v. 


o/ltE 


;.L*C  Kf.;-'  ■ 


,.i-‘ 


. jifk 

0 

^;-;  .'^j.r.t  J ."r  i- i f ■'%^lX',flt 


V 


.fioo 


•’‘  r ' i li  ‘j,  ' ■ -♦'•* 


. •'.;,  ^ j , -A^.-,,: 

■ "*  ' '“-r 

*-  I . * “^  * ’“  ■ ' ' •">  'i 


■)1« 


:.*  .);“.ci.'  )v " J.  '. f.'„ ' Xlij^ 


i¥ 

'.f  ^i?*!** 


. ::  : V ’ti  ••■ 


'•  ,/' 


Wi  /-■ 


y it-ni  .t:;-; 


’/  i 'Ti-v  » ■ V ■ ''  ’ 'OCT-*;  .flit 

.u  . . #4,  t jj  ■ ' 

I'-f  i ' , 


r -'r.  V. 


V w» 

■ , 


‘ i. .: 


f 


* ^ ■ ' ,. 

• ■ /•>v.“  •.  ; • •.  < • ■:  'iU-  i ' 

■.  ‘ ^ M*:  .;  '.'  u ■ y 

T ./  " "!;a', 

rr>:: 


kV:'. 


' >•  h'.  »4  - ,•  . f r» 


it  ; /•“>-t)'<.  C v‘-> :.  . 3;  *'. .‘,  't  i'X« 

/-  . • •t'^  ; 


t .'A- 


T“'.' 


o.-,-  i'  . 

. ' rf^>  1 ■ ;v  - “ -*■.  ■ t'iC 


1 •./( 

X .. 


-..:jr;, : 


'.0,  ,r-c , 

or  , \ 


y A O w - 


»;j’c.':.Crv  ':.  (7  f I -,.■  • >:^or; ett 

' .’  ' ■ " ' ':'' '.  ^ ,„c,''>'  ^ “'  '■■  ' .'■  .'  I 

}r.tp  :^r ,r,v ' j 

‘ ■ . * ' ■ ;*'  ■’■  ' ; 

. \ . I ,*  . ' 

. 0*'  c .j;  ' * \5 '•■  • '•■ 

Uxuic'.  •' ^ : a:-  >:  « ^ n'i'C  : 


>!L?rf  .-.  ',C'-^.,i.J!  i.  . ■'■  ,<-:■"  L iy* 


t.  ' ». 


o; 


:.  1:  T;-;! V- '■  • * - 

■r  ■— ?g"r  ' ' -'^  "^^“^•r--J^‘‘J  r 'rf-  t. 


...\ 
fti"  ' 


'.rmiiv'. 


-14- 

Experiment  tJ=6 

£93  grams  0(f  oinnamio  acid  were  added  to  4£5  cc  of  ab- 
solute ethyl  alcohol,  and  the  proeedure  carried  out  the  same  as  in 
experiment  §3,  114  oc  of  bromine  were  added  to  the  ester,  and 

638  grams  of  the  dibrom  ester  obtained.  This  was  of  the  the- 
oretical yield 

Experiment  ;f6a 

100  grams  of  the  dibrom  ester  v;ere  added  to  5C0  cc  of  alco- 
hol in  which  75  grams  of  potash  v/ere  dissolved.  The  reaction  mix- 
ture was  allowed  to  reflux  for  four  hours.  The  procedure  was  car- 
ried out  the  same  as  in  experiment  ;f4a.  41  grams  of  crude  phenyl 

propiolic  acid  were  obtained,  and  from  this  amount  18  grams  of  the 
pufe  acid. 

Experiment  f-6h 

ZOO  grams  of  the  dibrom  ester  were  added  to  880  cc  of  alco- 
hol in  v;hich  175  grams  of  potash  were  dissolved.  The  reaction  mix- 
ture was  refluxed  for  four  and  one  quarter  hours.  The  procedure 
was  carried  out  the  same  as  in  experiment  #4a.  1.11  the  phenjl- 

propiolic  acid  decomposed  into  phenylacetylene. 

Experiment  #6c 

100  grams  of  the  dibrom  ester  were  added  to  30C  cc  of  abso- 
lute alcohol  in  which  60  grams  of  potash  were  dissolved.  The  rec.6- 
tion  mixture  was  refluxed  for  six  hours.  The  procedure  was  carried 
out  the  same  as  in  experiment  #4a.  16  grams  of  pure  phenylpropio- 

lic  acid  were  obtained. 

Experiment  ^6d 

£00  grams  of  the  dibrom  ester  were  added-  to  600  cc  of  alco- 
hol in  v/hich  150  grams  of  potash  were  dissolved.  The  reaction 


r-TTT^  Y . 


W- 

■S?- 


’•  ;’. 


-S^’v  ufti'tvi'.Iv/* 


,i;<.  :..'  ....'*  otv£;,j  ',  -ji  r.  ' '}d  ;.•.('  ■•  . .'  -J  .V*: 

w 

' ■ r+  ■-..  “ - ,,  :coS^  " 


.1 


< .*:  1 > ;•:  f:iC  - rrc  .X'O^rTyi  ’'  ^ . 

_ <.-’i;!^'V  ^ --  f;,‘0'  "e  nt>  ■»'’JC/ 


• * -U 

.V.  0';lfJt0''J 


j » . J 


;c  '*, 


. '-’l;.!:.:  ,.C  ■:■  : ft  .iC’C'*-!  V-r 'U. 


i. 


0.  ^ X J ■'  vJ 

I 


r.;  ’-0 


(.'**■  '’ui.  ■’'  .'  o"::j  ' 'X'>. 
\ 


i.i..  .‘,  - t'  - 


:.'r 


CvT'  '’  ' ■’  «>».'.' '*'.’L'  :o  ..-.A 

i.'C.  . 


u,f-'  ie  i 


-.^£iti  ■: 


I 


v.:.::.^x.  ■ 

.l\*i.OC' !' -.i  I, 


; 4. 


r . I 


,■16-. 

. / *'  • 

';C'>.'. 

',.  ..c-i  X')  ' 

K 

•"  ' a .: 

t'  V' 

. 1. 

i Ic  \ 

i ' 

„ / ':'  ojr- 

► •»  r-  • .. 

’ 'rni.-v 

• .-  ■• -■  ,:r,f*  ut  ':"*  -' ' 

. .j  ..  * yur 

- ♦■,-<  ’-s 

,):  , t-ti:!:  -)Xa  <-u. >v’ 

t » 

01  j 

/ 

' V 

■■  J-\^ 

■ ■■  T ■ 

' '.*’  ’i'V*  ..  'v  • 

■ .■Si  f<-,; 

M 

i*’i'  •' 

■’.:  :'j.‘.  jr’f'i' ic  ' 

- h** 

' <V*  f ' 

! / 


I" 


" k I 


J 


,ll  • . I' 


r r 


,'A  •:  v.-iJ’  ;r:-  -.  ■.:  -0  R5'^^ 

Nti  V 5;)o»xnc :. "i  . r;io'j..  .’ 


> 


-0 


' ' ' " 


‘ ! 1;  ■ j.  \ ,...:' 

■:'".  c;f  '.••;•:•»  .'  '*»■•*;■•:•<•  ;0''X--  : '•  .}  i ^ '-<:  B 

. • ■ ■■  ’..•  .nlij  ri'i  .'•fr  ■:  ':■''  ■!  "I 

■ .* ' j,  Jr-  . .-ire  : J ’.  ‘f- ".'  j 


).  c 


.-1 


I 


/■: 


t ,0  Of:  ‘ r*  •"’ c '■  ' ' 

>*c  . .;'  ■■ 


.c:  r»4^  . . 


■: 


!.  .'  , . ,/,.  r-  .‘  'J-  ■'. 


-15- 


mixture  refluxed  for  four  hours.  The  procedure  was  carried  out  the 
same  as  in  experiment  #4a.  60.5  grams  of  the  pure  acid  were  obtain- 

ed. This  is  of  the  theoretical  yield. 

Experiment  #7 

£98  grams  of  cinnamic  acid  were  added  to  450cc  of  absolute 
alcohol.  The  procedure  was  carried  out  the  same  as  in  experiment 
number  S.  117  cc  of  bromine  were  added  to  tl^e  ester,  and  547 
grams  of  the  dibrom  ester  were  obtained.  This  was  80fj  of  the  tlie- 
oretical  yield. 

Experiment  #7a 

200  grams  of  the  dibrom  ester  were  added  to  600  cc  of  alco- 
hol in  which  150  grams  of  potash  were  dissolved  and  the  reaction 
mixture  was  refluxed  for  five  and  one  quarter  hours.  The  procedure 
carried  out  was  the  same  as  in  experiment  #5b  up  to  the  point  of 
recrystallization.  The  crude  acid  was  recrystallized  from  carbon 
tetrachloride.  Pure  white  crystals  were  formed  which  did  not  con- 
tain any  halogen.  21.5  grams  of  the  pure  acid  v/ere  obtained. 

Experiment  #7b 

100  grams  of  the  dibrom  ester  were  added  to  300  cc  of  alcohol 
in  which  75  grams  of  potash  v;ere  dissolved,  and  the  reaction  mix- 
ture refluxed  for  five  hours.  The  procedure  was  the  same  as  in  ex- 
periment #3b,  up  to  the  point  v;here  the  alcohol  was  distilled  off. 

At  this  ppint  the  potassium  salts  were  filtered  off,  and  hydrochlor- 
ic acid  added  to  the  solution  until  almost  neutral,  and  then  the 
alcohol  was  distilled  off  a This  eliminated  possibility  of  decom- 
position by  potash  at  this  point.  The  rest  of  the  procedure  was 
carried  out  as  before.  26.7  grams  of  pure  phenylpropiolio  acid 
were  obtained.  This  is  86.5^j  of  the  theoretical  yield. 


- '*^'•  ■»  “ 


isdAa 


.,.  -i 

• t;.-.  .•&C'*J  , . • '.;  : •'/-;■  <••■*  ftr-V  •• 


j 

;:Tfl  .:I!j 


- li  ^'■ 


-i  ixa  9 CUT 


. W-  't'v 


' -v# 


-i  ' 


If 

^i«i,  |f 


-T  4)  j:  ■/ 


J,'k  : i ■:::. 


•' t i's‘  “■■  y 


wi.i.  i3". 


f » • 

Ji.  i 


? ' ,1.  i’ ! ^ 


hIV  ’CI^-IS  ''L'l'i'irt'C  ■:.+■ 


'/r.  -i. 


ft;- 


V.' .. 


r> 

. :r  'o  ),.' 


. A . - 


-.J  ,'Ji 

i JvT'  ^*T  ■ 


•'  i I.  Ill  tl  i ,'' "l 


. C ■'(*,'  f ,1 


M • • 


I 

1 


'.T,  r*:vii‘vxO  {• 

■ % 


fS'  .•  ?•♦ 


- 'J 


Oit 


1 


_;c 


'f  I ,- 

■•\- 


r.c  J.  j't  ;<^)’i 


./•'V...C  / 


. i He.: 


.u 


i-  ' '■■ 


rc'Mooi 


, : '■  :*‘.r.;  . .'•r.O  i-r,i  'V' 

i • ■ j I ;>  <(■-.  ,-■  . f a..:;  i'rv  : ' ■'  ; I I , :•■ 

, % 

- .-J  • ...•.•;  ‘ . J yi’R  '.  I Vi  ■ o virr  v «•.;  • 

i.  iv ‘7’' : i ‘ '• 

'/  J '’T  i'  ' J.  J ’ .'  ■ ■.■'  ' i ' ^,'.1  i .'■f,  . 

I - • •/  J.'  : ) . .c'ti'.  t'i 


i,/  ■ » ' 


L..X 

» V-  . 


\ 


r:  .0 

. . I'T  ■ 

i..  ‘‘  , ■ ' ' * 'V ' ' ; 

•;  . ot, 

‘ f ' ' . '.' 

\Jt.  'iM 

'-’v'  .-'•  ■‘'’'Tc  r i 

• t-  t 

■ . :f  . 

T‘'»  '''.  rf«i.c  . .Vi 

■ -y- 

' 

■'  .■’1'  /.l.fXi 

I,;.;,'  ,,jrl  ,. . ;■ 

:i{  , 

lyiiu 

- ‘L'O  i'  .V 

»»  <• 

( 

•wr:;' 

'i.  ‘■■iJ:;  ' 

. ’ >*i'; '•? 

,.  ' >:  J.  .7  '.i'f.rj  • .’ 

•-  ':i'^ 

♦ 

7'.:'  n'o  ". 

■;f;7  :, ; a'rr^.'fec' 

" 'y  ’r-'  ■• 

■ 

t-,-. 

" ■•  -<  >'  ('  ■’  ' * 

•*"  ‘ ■*  t ,.  . . 

, . . • • ■•  - 

. Jl 

Ui.'  .j-L.iqt 


,v- 


\ 

! 


r uu':  .f  inq  pAiX‘,'f'  I 

■ . . . 'i 

•>  Oj  .0  i ‘ 


J 0.  e i 


} 


' .T.' i'li'-iC/J 

.-«.  . V 


J'  I 


! 


L I 


. /.  : (( t 


I* 


-16- 

3»  Preparation  of  the  Pthyl  Peter  of  ‘Phenylpropiolic  Acid<> 
Experiment  ^8 

6.8  grams  of  phenyl  propiolio  aetd  were  added  to  20cc  of 
absolute  ethyl  alcohol,  and  dry  hydrogen  chloride  was  passed  thro 
the  solution  until  completely  saturated,  and  then  the  solution 
was  allowed  to  stand  over  night  in  a stoppered  flask.  It  was  pour- 
ed into  250cc  of  ice  water  and  the  ester  separated  out  as  an  oil 
V7hich  was  separated  from  the  aquaeous  solution  hy  extraction  with 
ether.  The  ether  extract  was  washed  vdth  dilute  sodium  carbonate 
solution  until  the  aquaeous  layer  was  alkaline  to  litmus,  and  the 
excess  sodium  carbonate  was  removed  by  washing  with  water.  The 
ether  solution  was  dried  over  sodium  sulphate,  the  ether  evaporat- 
ed off,  and  the  ester  was  distilled  under  dirainished  pressure. 

At  21  mm  of  pressure  the  ester  was  distilled  over  at  160-163°0» 
About  5 grams  of  the  ester  were  obtained.  This  is  about  62. 
of  the  theoretical  yield. 

Experiment  #9 

23  grams  of  phenylpropiolie  acid  were  added  to  25cc  of 
absolute  ethyl  alcohol,  and  tho  procedure  carried  out  the  same  as 
in  experiment  #8.  At  13  mm  of  pressure  the  ester  distilled  over 
at  153-157°0.  About  15  grams  of  the  ester  were  obtained.  This  was 
55f^  of  the  theoretical  yield. 

Experiment  HlQ 

74  grams  of  phenylpropiolie  acid  were  added  to  75cc  of  ab- 
solute ethyl  alcohol  in  a 250  oc  flask,  and  lOcc  of  concentrated 
sulphuric  acid  were  added  to  the  mixture.  Another  flask  containin£ 
200  cc  of  absolute  aloohol  was  connected  to  the  25C  cc  flash, 
the  connecting  tube  passed  beneath  the  surface  of  the  acid  solu- 


-17- 


tion.  A fractionating  column  r.ncl  condenser  was  also  attached  to 
the  £50  cc  flask  which  was  heated  to  104-107°C.  The  absolute 
alcohol  in  the  other  flask  v/as  heated  gently  to  its  boiling  point 
so  that  it  took  one  hour  end  fifty  minutes  for  the  alcohol  vapors 
to  pass  through  the  solution.  The  vapors  absorbed  all  the  water 
that  was  formed  during  the  reaction,  and  the  then  diluted  alcohol 41 
was  constantly  being  fractionated  off  and  collected  at  the  dnd  of 
the  condenser.  3y  this  method  the  reaction  was  continually  being 
shifted  tov/ard  completion  so  that  it  did  not  come  to  the  same 
equilibrium.  The  ester  mixture  was  poured  into  ice  and  water  and 
the  rest  of  the  prodedute  carried  out  the  same  as  in  experiment  #8. 
The  ester  v;as  distilled  under  12mm  ijressure  at  153-155°C.  8C  grams 
of  the  pure  ester  were  obtained,  which  was  9lf  of  the  theoretical 
yield* 


-16- 


TV 

Tne  experiments  on  the  preparation  of  phenylpropiolic  aoid 
led  to  the  following  conclusions: 

1.  The  substitution  of  chloroform  for  ether  as  a hrominat- 
ing  medium  was  an  improvement  over  the  method  of  Perkin  since 
the  formation  of  lachrymating  substances  v/as  avoided. 

2.  Eemovsl  of  excess  bromine  by  means  of  sodium  bisulphite 
solution  gave  a purer  product. 

3.  The  concentration  of  the  alcoholic  potash  had  little  or 
no  effect  on  the  yields  of  phenylpropiolic  acid. 

4.  The  best  yield  were  obtained  when  one  and  one  half  times 
the  theoretical  amount  of  potash  was  added,  and  the  time  of  reac- 
tion was  five  hours. 

5.  Decomposition  of  potassium  phenylpropiolate  was  prevent- 
ed by  filtering  the  precipitated  salts  from  the  alcoholic  potash- 
solution,  neutralizing  the  filtrate  by  means  of  hydrochloric  acid, 
and  distilling  the  alcohol  from  the  neutral  solution. 

0.  Oarbon  tetrachloride  was  found  to  be  the  best  solvent 
for  the  recrystallization  of  phenylpropiolic  acid. 

The  experiments  in  the  preparation  of  the  ethyl  ester  of 
phenyl  propiolic  acid  led  to  the  follovnng  conclusions: 

1.  The  best  results  were  obtained  by  using  sulphuric  acid 

as  a catalyst,  and  passing  absolute  alcohol  vapors  through  the  mix- 
ture of  phenyl  propiolic  acid  and  absolute  alcohol,  maintaining 
the  temperature  near  100°C,  so  that  the  diluted  alcohol  vapors 
were  continually  distilled  off. 


^ o'.t  * ii 


'U’'  .1.^!  (- 


lL:ui 


I JJ 


.'  . . r. 


• ■-  (■ 


-'t 


'yi  T 


ui :trn  > 


1.  * 


' ti,  ’ ^3 


v-l't  ^■ 

'V. 

> 

'X’ ' r-:*' 

' '■'  ! ..  y'  "'ul.  !.' . 

• V * 

■ If  ■ 'h'X  'f  "7  ■ , '.  '. 

?A. 

. • ; • ' 

. '■  ';f'  »:'.(/ " ‘ ■' 

‘S’  •,!('. 

. ■'  -vii'.'v  : ft' A-  *.•••  t 0^-  V'  ii 

*V  t • ' 

6iu  '■.  ■ \i' 


} >1  J I'ljo.  {}•■£  *»■  '■  wJ*!//  - *T 


flU"5 •?"••■ 


■)Jr<riiA  » i/  j C'  Cr^  , T>*i.  r?  oj 


;<■  inih-f.;.'  -L'J' 


; ^ 


-19- 


y 

3IBLI0GPJIHIY 


1. 

J.  Aia.  cnem.  Soc.  (1910). 

32,  212 

2. 

J.  Chem.  Soc.  (1884),  45, 

415 

S. 

J.  Chem.  Soc.  (1908),  93, 

431 

3. 

Compt.  Rend.  (1907),  144, 

1281-83 

3*  (C.A.  (1907)  , 1,  2597 

4.  Ann.  (1870).  1^,  140 

5.  Ber.  (1883).  152 

6.  J.  Prakt.  Chem.  (1879).  (2)  20.  180 


7. 

J.  Chem.  Soc. 

(1884) , £5,  170 

8. 

Ber.  (1891). 

24,  4113 

9. 

Ber.  (1901), 

3648 

10. 

J.  Chem.  Soc. 

$1903),  83,  680,  1154 

11.  Proc.  Ckem.  Soc.  (1905).  67 

12.  Ber.  (1891),  2589 

13.  J.  Chem.  Soc.  (1884).  45.  174 


